Method of and apparatus for desulphurizing and fractionally separating petroleum



l v M. BENSON METHOD 0F AND APPARATUS FOR DESULPHURIZING AND FRACTIONALLY SEPARATING PETROLEUM Filed April '7, 1924 3 Sheets-Sheet 1 r w, w y 2 Y. m 0 u e ag y mf. AN uw LQSQAN I ww Tm T W@ w h M S 3 D vN @u M wm L9 N .M1 O T7, S E. N P1 E mn B A M mm Pl Ei SF Nov. 16 1926.

@www METHUD 0F AND APPARATUS FOR DESULPHURIZING A Nov. 16 1926. 1,607,043

M. BENSON METHOD 0F AND APPARATUS FOR DESULPHURIZING AND FRACTIONALLY SEPARATING PETROLEUM Filed April 7, 1924 ssheetS-snegt 5 U .lll .KWSN kw,

Patented Nov. 16, 1926.

UNITED STATES PATENT carica.

MARK BENSON, F LONDON, ENGLAND, ASSIGNOR TO THE CANADIAN AMERICAN FINANCE & TRADING COMPANY. LIMITED, OF VICTORIA, BRITISH COLUMBIA, CANADA, A CORPORATION OF BRITISH COLUMBIA. y i

METHOD OF AND APPARATUS FOR DESULPHURIZING- AND FRACTIONALLY SEPARAT- ING PETROLEUM.

Application led April 7,

Y preferably without precipitation of the bulk of the sulphur.

This invention contemplates the formation of vapor of composite character, containing both desired and undesired constituents, by intimate admixture with a liquid hydrocarbon (preferably under pressure) of superheated steam under pressure, and the immediate release of the pressure, with resulting expansion and substantially instantaneous vaporization oall orany desired part -of the volatile constituents in undecomposed form and the dispersion thereof in a relatively large volume of superheated steam vto form a composite steam-oil vapor 2 5 mixture, from which non-volatilized matter Ais segregated by the sudden expansion. The admixture of the steam and 011 may be advantageously effected by flowing the superheated steam against a solid or commnuted jet orspray of oil flowing counter-current thereto and under substantiall the same pressure as the steam. The de ydrogenating and cracking effect of vaporization by indirect heat transfer through catalytic surfaces of hivher temperature than initial temperature of the vapor mixture is avoided. l The composite steam-oil vapor mixture, after detrainment of contaminating and sulphur impregnated detritus, is subjected to a series of precipitations in stages by cooling in intimate contact with mechanically atomized condensate de osited therefrom. under conditions to whlch the, vapor mixture is at` the time subjected, and in intimate contact with mechanically atomized conden' v sate of lower dewpoint than the temperature of the vapor mixture being treated.

. Such treatment varies the surface tension vof' the liquid mixture, effects enrichment or 1924. serial No. 704,770. l

saturation of the vapor mixture by bein treated with hydrocarbon constituents o lower dewpoint, and effects preci itation of the hydrocarbon constituents of higher dewpoint without causing the formation of difficultly removable sulphur compounds, or the precipitation of relatively large amounts of I sulphurous vapors. The condensate of lower dewpoint is preferably puried by decantation before recirculationl to the preceding fractionating column.

This invention also contemplates the extraction from the steam-oil vapor mixture of water vapors between several stages of hydrocarbon precipitation in contact with hydrocarbon condensates. Such extraction, by limiting the volume of the expanding vaporfamixt-ure, checks the velocity of ow thereof, with consequent diminution of entrainment; effects the reduction of the excessive steam yratio resulting from the progressive extraction from the steam-oil vapor mixture of hydrocarbon constituents; avoids excessive dilution of the final hydrocarbon condensate; permits mechanical atomization of condensate in the fractionating columns without theexpenditure of excessive power; permits the'practice of my process'in apparatus of practicable size andl proportions,

vand increases the capacity of a plant of, given size. By my process, the steam-oil vapor mixture-,may have precipitated therefrom a condensate composed primarilyof hydrocarbons with but a slight amount of water, may thereafter have precipitated therefrom a condensate composed of alarge volume of water withl but a slight amount of hydrocarbons, and thereafter have precipitated vtherefrom a further condensatecomprised of a largev vohine of hydrcar-:L-

bons 'with but a slight amount of water.

By the hydrolysis due to the intimate repeated contact or mixture'of the hydrocarbon with the steam content of the vapor mlxture and the comparatively large volume of steam content of the mixture relativel to the hydrocarbon constituents,`the sulp ur compounds initially present in the petroleum are caused to form partially hydrolyzed compounds,` such as mercaptans,l

readily removable by washing with water or small amounts of known reagents. llf

' the initial temperature and volume of steam facilitated by 'exposure o are suiiicient, there is formed h drogen sulphide, which largely passes o condensible Gases and wash water and/or may be condensed... and removed from the condensate by small'quantities of known-reagents; such reaction apparently resulting from a reversible process which may be represented by the formula and the ratio employed being such. as to drive the equilibrium point of the reaction in the direction of` substantially increased hydrolysis. Hydrolysis 'ma if desired, be e the composite steam-'oil vapor mixture to small amounts of catalystslsuch as oxide of iron, bauxite or other alumina) without the deleterious effects lresulting from vaporization of the oil through or in the presence of catalysts.

The fractional precipitation of the hydrocarbon vapors Iin vintimate contact with i mechanically. atomized condensate produced under conditions to which the vapors are then subjected, and in intimate contact with mechanically atomized recirculated condensate of lower dewpoint, eHects such rectification of the fractionation due to condensation that, by a Lsingle continuous straight run operation, there are secured ymarketable products of Ls'u'ch definite and desired characteristics as to fit them for immediate use;

it being practicable to secure a water white gasoline of low sulphurv content l(say .04%) bya single distillationl from a Persian crude having. an initial sulphur contentV of 1%, which, when distilled andy redistilled in the usual manner with the aid of steam, yielded gasoline of .18% sulphur content.

` unaffected by treatment with such a smal l.amount of sulphur removal.

quantity of'fuming oil of vitriol, neutralization and washing, and required several treatments with large :quantities of sodium hypoehlorite, soda and water to effect the same I A gas and lubricating oil fraction of ravity .792 produced by my method from ersia-n crude oil contained only .4% sulphur, while a gas and f lubricating oil` fraction of gravity .7 92 pro-- duced from. such Persian crude by distilla- [tion` in the usual manner with the aid of with non-v Leonesa steam contained 1.2% sulphur inthe form of diflicultlyl removable. organic sulphurJ compounds. ln another instance, the same amount of sulphur Was removed from dis-y tillate produced by my method by washing '70 once with normal hypochlorite, followed by neutralization and water washing, as. was removed from oil produced from the same crudev byusual methods by twice washing with'tri-normal hypochlorite and soda and once washing with 2% of fuming oil of Vitriol, each treatment being followed by neutralization and water washing.

The intimate contact between the steamoil vapor mixture and condensates of different dewpoints, to augment and accelerate the coaction thereof, is primarily effected vby minutely subdividing and eifectin rapid movement by mechanical means of tie particles of condensates so that they are' virtally held in suspension, somewhat like a mist or fog, and present the maximum area or reacting surfaces between the vapor mix- A ture and condensates. The` repeated minutey dispersion .of the condensates promotes the absorption by the vapors from the recirculated condensates of constituents of low dewpoint and the deposition from the vapors of constituents of high dewpoint; i's believed to facilitate by repeated contact with steam the hydrolysis of the initial sulphur compounds present in the oil and production of mercaptans arid hydrogen sulphides; l

and 'permits the treatment of large volumes of material relatively to the size of the fractionating columns.` The recirculation and mechanical atomization of the condensate of lower dewpoint in the path of the steam-oil vapor mixture permits accurate control of the breadth of cut and causes such differences in the surface tensions of the hydro` carbon and water constituents of the vapor mixture as to permit waterj vapor'prec1pi,

tation without substantial orV deleterious vhydrocarbon precipitation between the stages of hydrocarbon precipitation in contact with atomized condensates.

The` accompanying drawings illustrateA i the layout of a plant for the practice of our process for the 'production of commercial petroleum fractions in a single distilling operation.

; In the drawings, Fig. 1 is a diagrammatic side elevation, partly in section, of a plant desicned for the practice of my process; andbFig. 2 is a diagrammatic plan view of the same, parts being omitted for thefsa-ke of better illustration; Fig. 3 is an enlarge',

vertical sectional view4 of the separator shown in Figs. 1 and 2; andFi 4 is anmen# n' larged vertical sectional view o a fractlonating column.

In the operation of the plant illustrated" in the dr'awlngs, petroleum delivered by a-V conduit passes throu h a suitable lilter 11 to a pump 12, b whic it is forced under pressure through tie conduit sections 13 and the tubes of the economizing heat exchangersl 14, 15,16, 17 and 18. If desired, the latent heat of condensation in one or more of the condenser-s 56', 56, 56', hereinafter described, may b e utilized by by-passing oil therethrough by means of valve controlled branch pipes .13', and the preheated oil discharged from the heat exchangers may, if desired, be further preheated by a preheater 19 to which saturated steam is admitted under control of a valve' 2O.

The preheated oil, in liquid form, is discharged as a solid' or comminutedl jet from the last conduit section 13, under control of a valve 21, into a mixer 22, preferably of the injector type, and a jet of superheated steam is discharged into the mixer countercurrent to the oil jet from the conduit 23 under control of a valve 23, the two fluids being discharged under. substantially the same pressure. The mixing chamber or injector freely discharges, through the tube 24, tangentially into the peripheral chamber 25 of a separator 26, whereby the steamoil mixture is immediately expanded and its pressure reduced (preferably below twenty pounds and as near atmospheric pressure as is compatible with economic operation) with resulting substantially instantaneous -vaporization of the volatile hydrocarbon constituents without cracking; the temperature of the preheating surfaces being maintained below the initial temperature of the steam-oil vapor mixture. The tangential discharge and the expansion of the mixture gives it a whirling action and results in de-l position of unvaporized particles, with adhering sulphur, on the conical bottom 26 of the separator 26, from which such products maybe removed by way of a suitable trap.

The steam-oil vapor mixture escapes from the peripheral chamber 25 of the separator through the axial flue 27 into a chamber 27 from which it escapes through vent pipesv 28 extending upward from the diaphragm 28 into a friction bell or eliminator 29 comprising a drum having an open bottom and closed top from which depend a plurality of nested side walls/29 which are partially submerged in a liquid seal contained in the bottom ofthe chamber 30. Each wall of the drum contains small perforations 31 staggered relatively to the perforations in the adjacent walls so that the vapors passingl through the eliminator have their direction of flow repeatedly and sharply changed and the exposed areas of the perforated walls are automatically variable (proportionatelv to changes in the velocity and in the slight pressure of the vapor mixture) by means of the counterweight 32 t connected with the drum bymeans of a bension member 32. passing through a liquid seal-32". j

Unvaporized particles or mist entrained with the steam-oil vapor are detrained\by the eliminator and discharged from the bottom thereof through the trapped pipe 33 into the peripheral chamber 25 of the sep arator 26.

The steam-oil vapor mixture, substan-l tially freed from mist or unvaporized liquid particles, is discharged 'through the conduit 34 into the 'rst of a series of similar fractionating columns 35, 35, 35", 35, 35,

35e having means for mechanically atomizing therein condensate to form a mist or fog of highly dispersed liquidl particles in the path of. the vapor and for recollecting the dispersed liquid. Such atomization and recollection may be effected by apparatus of known type, but I have found an adaptation of the Feld scrubber most advantageous and have shown it herein for the sake of illustration.

The steam-oil vapor mixture entering the.

fractionating column 35 flows through the passages 36 between the pans 37 and baffles or drip boards 38 while there are projected across these passages sprays or atomized particles of liquid condensate. Such .condensate is picked up from the pans and projected at high velocity across the passages by the cones 39 of usual Feld type which are rapidly rotated by thev power driven shaft Conical bailie plates 41 and 42 are fixed in the upper part of the column 3 5 to detrain from the vapor mixture atomized condensate or mist carried thereby, and further.

tial respects to the eliminator 29, and to the series of eliminators 43a, 43", 43, 43d and 43e 'connected with theV respective fractionating columns by conduits 44, 44", 44, 44d and 44 and passages 45, 45", 45, 45d and 45@z The passage of the steam-oil vapor mixture through the column 35 and through the -atomized condensate or mist therein effects precipitation from thefl -vapor mixture of high dew point condensate, whlch 1s collected in the pans 37 Such precipitation 1s 'facilitated and the fractionation rectified by the return to the column 35 of cooler hydrocarbon condensate from the similar column 35. Such rectifying condensate is pumped from the receiver 46a (supplied from the column 35a) by the pump 47 through the pipe 48 into a regulator 49, from which condensate passes through the pipe 50 into the top of the column 35 under control of the' 'valve 51. Any excess of .oil pumped to the regulator 49 is returned to the'ireceiver 46a' through the pipe 52.

The rectifying condensate supplied to the top of the column 35 is atomized or sprayed by the cone mechanisms described. l Any constituentsof the rectifying condensate 'within the dew point of the condensate in the column 35 but which may have been carried therefrom by entrainment are collected `by the pans 37 and retained in the column 35 '15 after having served to cool the vapor mixture passing through the column. Constituents of the returned rectifying condensate which have lower dew points than the temperature of the vapor mixture in the column 35 are vaporized by such mixture and cause precipitation therefrom of higher dew point condensates by reason of the heat or energy consumed in effecting such vaporization.

Continued precipitation of hydrocarbons of high dew point causes accumulations of condensates in the pans 37 which overflow into the bottom of the column, from which they are withdrawn through the adjustable liquid sealed trap 53 into the receiver 46.

Sf-This condensate, which inthe operation illus- `4C there is precipitated from the vapor condensate of the next lower dew point desired. Such precipitation is facilitated and the fractionation rectified by the return to the column a of condensate of lower dew point from the column 35".

The columns 35, 35, 35", 35, 35, 35 and their connected parts are all similar in construction and operation tothe column 35 and its connected parts and discharge fractions of various dew points and characteristics through adjustable liquid sealed traps, receivers, heat exchangers and coolers to desired points. :In the plant illustrated, the condensate discharged from the column 35 will be heavy lubricating base oil; that discharged from the column 35a will be heav oil and paratline; that discharged from co umn 35b will be gas oil; that discharged from the column 35c will be heavy kerosene;

that discharged from the column 35d will be light kerosene and' that discharged from the column 35e will be water-white gas'olene.

When the precipitation of hydrocarbon .constituentsv from the steam-oil vapor mixvture has been carried -to such extent `as to leave-in 'the mixture an excess of water vapor, or when water vapor begins to -precipitate in substantial quantities in thefractionating columns, there is inserted in the vapor` mixture conduits between appropriate columns the Water-vapor condensers 5 6', 56"

and 56l through which oil flowing' to the mixer lor other cooling Huid may be circuf lated in contact with vapor carrying tubes.v JOwing to the differences in dew polnt4 and in "the surface tensions imposed by the treatment described upon the hydrocarbon constituents and the water-vapor constituents pipes 59, 59", 59. tothe columns whence the vapor came.

When water vapor begins to precipitate in and receivers,l such decanters discharging the condensed water through trapped outlets 61, 61, 61d, 6:1e and the condensed hydrocarbons flowing from the tops of the decanters to the adjacent receivers, so that no water-is recirculated with the recirculated-rectifying condensate. p J

Since there are no hydrocarbon condensates of lower dew point wherewith to cool and rectify the vapor mixture flowing through the column 35", it may be desirable to supply water to the regulator 49e of this column to eiiicientlycool the vapor mixture in the column. Uncondensed hydrocarbons, if any, flowing from this column through the conduit 56 may be absorbed in a sultable absorbent, collected as gases or wasted to the atmosphere.

`the vfractionating columns, decanters 60", 60, (30,60e may be interposed between the trapsv If desired, suitablenreagents may be incolumns, as,

troduced into the fractionatin connections for instance, through valve 'wahthe tubes 5o, 50a, 50h, 50, 50d, 5oe to 1' wash out sulphur compounds or for any desired purpose. By appropriate introduction into the columns of Suitable reagents, sulphuric acid, lor sodium hypochlorite, theA hydrocarbons condensing from the distillates may be refined and the redissolving of Sul- \phur compounds prevented.

In the drawing, for simplicity and clarity vof illustration, the outlet traps vare shown outside of and below the fractionating col- ,l

' umns,but in some cases it is advisable to s within the columns to conplace such tra urthermore, wlnlecthe receivserve heat.

ers 46-46 are shown above and before the 'heat exchangers 18-14, the'postions of these parts may be reversed so that the rectifying condensate returned to the next preceding column 'will be further cooled. v

For topping operations, the plant illustrated may be provided with a supplementary mixer 22 and separator 26 discharging through an eliminator 28 into the fractionating vcolumn 35.' Such supplementary mixer, separator and eliminator may be usedy with a comparatively small amount of steam at comparatively low temperature and in conjunction with the fractionating columns 35, 35d and 35 to separate the constituentscommonly combined as once run distillate. The heavier constituents of the crude will, in such operations, be unvaporized and may be discharged as fuel oil or for further treatment through the trapped bottom 27 of the supplementary separator.

In the operation of a plant such as shown in the drawings, for complete fractionation of the oil, it has been found desirable to preheat the oil as much as possible without raising the temperature of the preheating surfaces above the temperature of the ensuing steam-oil vapor mixture and without cracking or dehydrogenating the oil. In treating Persian crude oil, steam may be introduced into the mixer 22 at a temperature of from 750 to 1000 degrees F. at a pressure of say 150 pounds and oil at a temperature of say 200 to 300 degrees F. and under a pressure imposed by the pump 12 of say 150 pounds. Under such conditions, satisfactory fractionation and satisfactory desul phurization without the use of catalysts, are obtained, without cracking, by the introduction of .9 part by weight of steam per part by weight of oil, though an increase in the temperature and volume of steam was found to improve desulplurization without-crackmg. v It will, however, be understood that the quantity, pressure, and temperature of the superheated steam and the pressure and temperature of the oil introduced intov the mixer will be-regulated in accordance with the character of the oilv under treatment and the product desired.

A primary advantage of my process is the avoidance of any necessity for cracking, and the recovery in fractionated form of substantiallythe theoretical content of the crude of the desired fractions, lthe fractionation bein feffected with but a single vaporization e ected by the use of supcrheated steam, to achieve maximum desul'phurization. The use of my process greatly diminishes the size and cost of the plant required and permits the continuous operation of the plant, since there are no still bottoms to burn out or require cleaning;.reduces the wear, tear and danger commonly mcident to the operations of a refinery since there is no fire near the, oil and exposure to gas poisoning is eliminated; and also greatly reduces the usual distilling and refining losses, While permitting great flexibilit in the operation of the plant and the pro ucts secured.

Having described my invention, I claim:

1. The method of treating petro1eum` which 4comprises the vaporization thereof by direct admixture of super-heated steam there- .with and immediate expansion of the mixture, and simultaneously precipitating from the resultant mixture of vapor and steam hydrocarbon constituents and enriching the hydrocarbon content of the mixture by contact with mechanically atomized hydrocarbon condensate.

2. The method of treating petroleum which comprises the formation of an oilsteam vapor, and precipitating hydrocarbons from said vapor in stages, precipitation in one stage being effected in intimate'contact with mechanically atomized condensate of another stage.

3. The method ofdesulphurizing mineral oils which comprises vaporization thereof by. direct admixture of superheated steam therewith and immediate expansion of the oilsteam mixture, and precipitation of hydrocarbon constituents thereof in intimate contact with mechanically atomized condensate therefrom.

4. The methodV of treating `petroleum which com rises the formation of an oilsteam vapor, precipitatinghydrocarbon constituents while the vapor is in intimate contact with mechanically atomized condensate deposited under conditions to which the vapor is then being subjected and in intimate contact with mechanically atomized condensate deposited in alater stage under lower temperature conditions than those to which the vapor is then being subjected.

5. The method of treating steam-mineraloil vapors which consists in varying the relative surface tension of its constituents by intimate contact with mechanically atomized hydrocarbon condensate and condensing from the mixture water vapor without substantial condensation therewith of hydrocarbon constituents.

6. In the art of refining petroleum,- the` 8. The method of fractionally separating and desulphurizing petroleum, Which comprises Vaporizing the liquid petroleum Without cracking by direct admixture with super- 5 heated steam and Without exposure to heating surfaces higher temperature than the `\\initia'l tempeiature of the mixture, detraining unvaphrized particles from the mixture', condensing the mixture in stageslin intimate moaoasf Contact With a mist of mechanically atomzed '1*0 petroleum condensate, detraining from the mixture between condensing stagesmistentrained therewith, 'and mechanically atomizing condensate 'precipitated in one stage in the ath of mixture/in another'stage. .15

In Witness whereof, I have hereunto'set my name this 17thv day of March, 1924:.v

l MARK BENSON. 

